Methoxymethylfurfural

Last updated
Methoxymethylfurfural
Methoxymethylfurfural.svg
Names
Preferred IUPAC name
5-[(Methoxy)methyl]furan-2-carbaldehyde
Other names
5-Methoxymethyl furfural; Methoxymethylfurfurol; 5-(Methoxymethyl)furan-2-carbaldehyde; 5-Methoxymethyl-2-furfural; 5-(Methoxymethyl)-2-furaldehyde
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.149.478 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C7H8O3/c1-9-5-7-3-2-6(4-8)10-7/h2-4H,5H2,1H3
  • O=Cc1oc(cc1)COC
  • COCC1=CC=C(O1)C=O
Properties
C7H8O3
Molar mass 140.138 g·mol−1
AppearanceColorless liquid
Density 1140 kg/m3
Melting point −8 °C (18 °F; 265 K)
Boiling point 109 to 111 °C (228 to 232 °F; 382 to 384 K) at 11-12 tor
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Skin irritation/Skin sensitizer
Related compounds
Related furan-2-carbaldehydes
 Furfural
Hydroxymethylfurfural
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Methoxymethylfurfural (MMF or 5-methoxymethylfuran-2-carbaldehyde) is an organic compound derived from dehydration of sugars and subsequent etherification with methanol. [1] This colorless liquid is soluble in a wide range of solvents including lower alcohols. The molecule is a derivative of furan, containing both aldehyde and ether (methoxymethyl) functional groups. MMF has been detected in the leaves and roots of Chilean Jaborosa magellanica (Solanaceae). [2] It has a typical odor suggestive of maraschino cherries. [3] MMF can be made from a wide range of carbohydrate containing feedstocks including sugar, starch and cellulose using a chemical catalytic process and is a potential "carbon-neutral" feedstock for fuels and chemicals.

Contents

Production

Related to the production of furfural, MMF can be produced from C-6 sugars hexoses such as glucose and fructose. It is formed via the dehydration of the hexoses and subsequent etherification of hydroxymethylfurfural (HMF). [1] Already in 1936 a batch process was patented for the production of MMF and methyl levulinate. [4] Bicker reported first order kinetics for the dehydration of fructose, etherification of HMF into MMF and by-products formation in methanol. [5] An MMF yield of 78% at 99% conversion was obtained at 240 °C and a residence time of 2 s. At short residence times, especially at lower temperatures significant amounts of HMF were observed and smaller amount of MMF. The amount of MMF increased with residence time at the cost of the amount of HMF, which indicates that MMF formation goes through HMF. Reactions in various alcohols by Brown et al. led to the formation of the appropriate HMF ether and levulinic acid ester. [6] A number of primary and secondary alcohols was tested, from methanol to 2-butanol. In methanol a yield of 43% MMF was reported in combination with 47% methyl levulinate. Garves has shown that also cellulose is efficiently degraded by alcohols and strong acid-catalysts at 180 °C to 200 °C within minutes. In methanol methylglucosides, MMF and methyl levulinates plus methyl formates are formed in consecutive reactions, accompanied by some humic residues. [7]

Uses

The synthesis of novel biomass-based vinyl polymers from 5-methoxymethyl furfural as the starting material was described by Yoshida. [7] HMF and MMF are also key molecules into the conversion of liquid biofuels. HMF and MMF can be converted to a wide range of mono- and dialkoxymethyl ethers. [8] The compounds can also further converted to 2,5-dimethylfuran (DMF) and valeric biofuels. [9] Oxidation of MMF results in the formation of 2,5-furandicarboxylic acid, which has been proposed as a replacement of terephthalic acid for the production of a wide range of plastics including polyesters and polyamides. The potential applications of furan based building blocks for polymer applications has been extensively reviewed by Gandini. [10] Patents have appeared that MMF prevents the growth of fungi in leathers, paints, foods and fabrics [11] and that MMF as a part of a much broader spectrum of active compounds is effective against cardio, cerebro-vascular and Alzheimer's diseases and depression. [12] The addition of MMF and other alkoxymethyl furfurals to a tobacco product has been patented because it acts as a fragrance to provide a sweet flavor in the smoke. [3]

As an ingredient in food

Unlike HMF, MMF has not been found to a major extent in natural products and in food items. However, Podesta has shown that MMF is a constituent of the leaves and roots of Chilean Jaborosa magellanica (Griseb.) Dusen (Solanaceae). MMF occurs at concentrations of 5 mg MMF per kg dried roots and leaves. It was also present as a component of the roots of Asparagus cochinchinesis and Asparagus lucidus, however it was assumed that the A. lucidus product had been formed as an artifact from fructose during the isolation process. [2] On the contrary EMF, the ethanol ether of HMF can be found in many alcoholic beverages such as beer and wine, especially those who still contain high sugar levels at the end of the fermentation. [1]

Toxicity

It has been claimed that 5-methoxymethyl-2-furaldehyde prevents the growth of fungi in leathers, paints, foods and fabrics. [11] However, the first phase of REACH testing has shown that the oral LD50 value of MMF in Wistar rats was established to exceed 2000 mg/kg body weight. According to the Regulation (EC) No 1272/2008 on classification, labelling and packaging of substances and mixtures, MMF does not have to be classified and has no obligatory labelling requirement for oral toxicity. It was found that MMF gave positive results in the skin irritation test and should be classified as a skin sensitizer.

Quantification

MMF UV MMF UV.JPG
MMF UV

MMF can be quantified by using both GC and HPLC. MMF can routinely been analyzed on a GC using for example a Varian VF-WAXms column with a temperature profile up to 250˚C and FID detector. When analyzed by HPLC it can be quantified by UV. In the picture below the UV spectrum is shown. The peak maximum in methanol is at 279.5 nm (Molar extinction coefficient ε 13854 M−1.cm−1).

The IR sample below was recorded on a Nicolet 6700 FT-IR at room temperature using the liquid film (diamond ATR-cell) procedure.

MMF IR with annotation.JPG

History

The first publication on MMF dates from 1927, by Haworth et al., in which it was observed as a product of tetramethylfructose dehydration in an attempt to deduce the structure of sucrose. [13] Already in 1936 a German patent was published on the production of MMF from fructose. [4] It was later also synthesised by Wolfrom et al. from tetramethyl glucoseen. Both substrates showed an efficient conversion into MMF under aqueous acidic conditions. [14] The first claims for industrial applications arose in the sixties. [3] [11]

Related Research Articles

In chemistry, a pentose is a monosaccharide with five carbon atoms. The chemical formula of all pentoses is C
5H
10O
5, and their molecular weight is 150.13 g/mol.

Petrochemical Chemical product derived from petroleum

Petrochemicals are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable sources such as maize, palm fruit or sugar cane.

Tetrahydrofuran Chemical compound

Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water-miscible organic liquid with low viscosity. It is mainly used as a precursor to polymers. Being polar and having a wide liquid range, THF is a versatile solvent.

Furfural is an organic compound with the formula C4H3OCHO. It is a colorless liquid, although commercial samples are often brown. It has an aldehyde group attached to the 2-position of furan. It is a product of the dehydration of sugars, as occurs in a variety of agricultural byproducts, including corncobs, oat, wheat bran, and sawdust. The name furfural comes from the Latin word furfur, meaning bran, referring to its usual source. Furfural is only derived from lignocellulosic biomass, i.e., its origin is non-food or non-coal/oil based. Aside from ethanol, acetic acid and sugar it is one of the oldest renewable chemicals. It is also found in many processed foods and beverages.

Furan is a heterocyclic organic compound, consisting of a five-membered aromatic ring with four carbon atoms and one oxygen atom. Chemical compounds containing such rings are also referred to as furans.

Molischs test

Molisch's test is a sensitive chemical test, named after Austrian botanist Hans Molisch, for the presence of carbohydrates, based on the dehydration of the carbohydrate by sulfuric acid or hydrochloric acid to produce an aldehyde, which condenses with two molecules of a phenol, resulting in a violet ring.

Humins are carbon-based macromolecular substances, that can be found in soil chemistry or as a by-product from saccharide-based biorefinery processes.

Isosorbide Chemical compound

Isosorbide is a bicyclic chemical compound from the group of diols and the oxygen-containing heterocycles, containing two fused furan rings. The starting material for isosorbide is D-sorbitol, which is obtained by catalytic hydrogenation of D-glucose, which is in turn produced by hydrolysis of starch. Isosorbide is discussed as a plant-based platform chemical from which biodegradable derivatives of various functionality can be obtained.

Hydroxymethylfurfural Chemical compound

Hydroxymethylfurfural (HMF), also 5-(hydroxymethyl)furfural, is an organic compound formed by the dehydration of reducing sugars. It is a white low-melting solid which is highly soluble in both water and organic solvents. The molecule consists of a furan ring, containing both aldehyde and alcohol functional groups.

Levulinic acid Chemical compound

Levulinic acid, or 4-oxopentanoic acid, is an organic compound with the formula CH3C(O)CH2CH2CO2H. It is classified as a keto acid. This white crystalline solid is soluble in water and polar organic solvents. It is derived from degradation of cellulose and is a potential precursor to biofuels, such as ethyl levulinate.

Furfuryl alcohol Chemical compound

Furfuryl alcohol is an organic compound containing a furan substituted with a hydroxymethyl group. It is a colorless liquid, but aged samples appear amber. It possesses a faint odor of burning and a bitter taste. It is miscible with but unstable in water. It is soluble in common organic solvents.

Chloroalkyl ethers are a class of organic compounds with the general structure R-O-(CH2)n-Cl, characterized as an ether connected to a chloromethyl group via an alkane chain.

Methyl acrylate Chemical compound

Methyl acrylate is an organic compound, more accurately the methyl ester of acrylic acid. It is a colourless liquid with a characteristic acrid odor. It is mainly produced to make acrylate fiber, which is used to weave synthetic carpets. It is also a reagent in the synthesis of various pharmaceutical intermediates.

<i>gamma</i>-Valerolactone Chemical compound

γ-Valerolactone (GVL) is an organic compound with the formula C5H8O2. This colourless liquid is one of the more common lactones. GVL is chiral but is usually used as the racemate. It is readily obtained from cellulosic biomass and is a potential fuel and green solvent.

2,5-Furandicarboxylic acid Chemical compound

2,5-Furandicarboxylic acid (FDCA) is an organic chemical compound consisting of two carboxylic acid groups attached to a central furan ring. It was first reported as dehydromucic acid by Rudolph Fittig and Heinzelmann in 1876, who produced it via the action of concentrated hydrobromic acid upon mucic acid. It can be produced from certain carbohydrates and as such is a renewable resource, it was identified by the US Department of Energy as one of 12 priority chemicals for establishing the “green” chemistry industry of the future. Furan-2,5-dicarboxylic acid (FDCA) has been suggested as an important renewable building block because it can substitute for terephthalic acid (PTA) in the production of polyesters and other current polymers containing an aromatic moiety.

2,5-Bis(hydroxymethyl)furan Chemical compound

2,5-Bis(hydroxymethyl)furan (BHMF) is a heterocyclic organic compound, and is a derivative of a broader class of compounds known as furans. It is produced from cellulose and has received attention as a biofeedstock. It is a white solid, although commercial samples can appear yellowish or tan.

Methyl vinyl ether is an organic compound with the chemical formula CH3OCH=CH2. A colorless gas, it is the simplest enol ether. It is used as a synthetic building block, as is the related compound ethyl vinyl ether (a liquid at room temperature).

2,2-Di-2-furylpropane Chemical compound

2,2-Di-2-furylpropane is a condensation product of furan and acetone. It is a relatively high boiling liquid and is a precursor to the rubber additive bis(tetrahydrofuryl)propane used in the manufacture of high vinyl content rubber for high performance tires.

Allyl glycidyl ether Chemical compound

Allyl glycidyl ether is an organic compound used in adhesives and sealants and as a monomer for polymerization reactions. It is formally the condensation product of allyl alcohol and glycidol via an ether linkage. Because it contains both an alkene and an epoxide group, either group can be reacted selectively to yield a product where the other functional group remains intact for future reactions.

Furan resin

Furan resin refers to polymers produced from various furan compounds, of which the most common starting materials are furfuryl alcohol and furfural. In the resin and in the cured polyfurfurol, the furan rings are not connected by conjugation. The resins are generally used as binders for sand castings. The furan monomer is typically converted to a free-flowing resin with mild acid catalysis. Curing is achieved using strong acid.

References

  1. 1 2 3 van Putten, R-J., van der Waal J.C. de Jong, E., Rasrendra C.B., Heeres, E.J. and de Vries HG. (2011) Furan-based platform chemicals of the future. Dehydration of hexoses as biosustainable product route. Chemical Reviews submitted.
  2. 1 2 Podesta, Federico; Fajardo, Victor; Freyer, Alan J.; Shamma, Maurice (1988). "5-Methoxymethyl-2-furaldehyde: A Natural Furanoid fromJaborosa Magellanica (Solanaceae) 5-Methoxymethyl-furfural: Ein natürliches Furanoid ausJaborosa magellanica (Colanaceae)". Archiv der Pharmazie. 321 (12): 949. doi:10.1002/ardp.19883211225. S2CID   86420362.
  3. 1 2 3 Hind, J.D. and Crayton, F.H. (1963) Tobacco flavorants. US 3,095,882
  4. 1 2 Sprengler, O., Weidenhagen, R. and Korotkyj, B. DE632322 Verfahren zur Herstellung von Alkoxymethylfurfurolen und Lävulinsäurealkylestern
  5. ↑ Bicker, M., Kaiser, D., Ott, L. and Vogel, H. (2005) Journal of Supercritical Fluids 36, 118-126.
  6. ↑ Brown, D.W., Floyd, A. J., Kinsman, R. G., Roshan-Ali, Y. (19ė82) J. Chem. Tech. Biotechnol. 32, 920-924.
  7. 1 2 Yoshida, Naoki; Kasuya, Natsuki; Haga, Naoki; Fukuda, Kiyoharu (2008). "Brand-new Biomass-based Vinyl Polymers from 5-Hydroxymethylfurfural". Polymer Journal. 40 (12): 1164. doi: 10.1295/polymj.PJ2008170 .
  8. ↑ Gruter, G.J., de Jong, E. (2009) Biofuels Technol., 1, 11-17; Gruter G-J.M., Dautzenberg, F. W.O. patent 2007/104515, 2007; Gruter G-J.M., Dautzenberg, F. E.P. patent 1,834,950, 2007; Gruter G-J.M., de Jong, E. W.O. patent 2009/141166, 2009; Gruter G-J.M., de Jong, E. E.P. patent 2128227, 2009; Gruter G-J.M., E.P. patent 2034005, 2009; Gruter G-J.M. U.S. Patent 2010212218, 2010.
  9. ↑ Bond J.Q, Martin Alonso, D. Wang, D, West, R.M, Dumesic. J.A. (2010) Integrated catalytic conversion of g-valerolactone to liquid alkanes for transportation fuels. Science 1110-1114: Huber, G.W, Iborra, S, Corma, A. (2006) Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering. Chemical Reviews, 106 (9), 4044-4098.
  10. ↑ Gandini, A., Belgacem, N.M. Prog. Polym. Sci., 1997, 22, 1203-1379; Gandini, A., Silvestre, A.J.D., Pascoal Neto, C. Sousa, A.F., Gomes, M. J. Pol. Sci.: Part A: Pol. Chem., 2009, 47, 295–298; Gandini, A. Pol. Chem. 1, 245-251.
  11. 1 2 3 Constantin, J.M., Humphreys, T.W. Lange, H.B. Shew, D. and Wagner, J.R. (1963) US. Patent 3,080,279, Mar. 5, 1963.
  12. ↑ Tashiro, R and Pater R.H. 1996 Compositions and method of treating cardio, cerebro-vascular and alzheimers diseases and depression. US5589182
  13. ↑ Haworth, W.N., Hirst, E.L. Nicholson, V.S. (1927) J. Chem. Soc. 1513.
  14. ↑ Wolfrom, M. L., Wallace, E. G., Metcalf, E. A. (1942) J. Am. Chem. Soc. 64, 265-269.
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